【作者】 王惠钢；

【导师】 郑小明； 陈平；

【作者基本信息】 浙江大学 ， 有机催化， 2004， 博士

【摘要】 近几年来,具有核壳结构的自组装系统的研究在国内外是一个十分活跃的领域,随着对核壳结构聚合物微球研究的深入,空心聚合物微球胶囊的研究也引起人们的广泛关注。由于超分子是指各物种间通过非共价键缔结而成的具有特定的结构和功能的亚稳态体系,而聚合物结构是通过缩聚,以共价键结合而形成的稳定的分子体系,因此超分子结构的非共价相互作用的稳定性是有限的,极易导致结构的改变。聚合物结构的空心纳米胶囊除保持了纳米颗粒原有的特性外,还由于规则排列的纳米颗粒间的耦合作用而使得胶囊具有一些特殊的性质,而且其表面性质可以通过有机改性反应进行结构修饰。纳米胶囊的应用领域非常广泛,已经或正在应用于微型反应器、药物载体、染料分散剂、非均相催化剂载体等方面。本论文的主要研究工作是提出了结合乳液模板聚合-渗透溶胀技术的方法,并通过该方法成功合成了聚硅氧烷空心纳米胶囊,进行了一系列的结构功能化研究,并利用不同官能团与钯的配合物作为催化剂研究考察了在催化Heck偶联反应中的性能。本论文提出并运用乳液聚合的模板方法和渗透溶胀技术相结合的方法制备合成了聚硅氧烷纳米胶囊,并采用Stober方法对该合成方法进行了改进。系统研究了聚硅氧烷空心纳米胶囊的结构和形貌,首次合成了多种具有不同表面属性(各种官能基团)的聚硅氧烷空心纳米胶囊,通过对硅氧烷分子官能团及聚有机硅分子链的结构和性质的分析,探讨了聚硅氧烷空心纳米胶囊的结构与其理化性能间的关系,同时也率先合成了聚硅氧烷空心纳米胶囊固载钯配合物,研究考察了作为新型的负载型载体在催化中的应用。本论文的主要内容如下:第一部分综述了纳米胶囊的研究结果及其应用。按纳米胶囊的制备方法归类,阐述了纳米胶囊的国内外研究进展以及每种制备方法的特点和优缺点。第二部分为论文涉及的一些有机硅单体的合成研究,考察和总结了氯硅烷甲醇醇解的一般规律。阐明了在醇解反应过程中所产生的HCl是发生副反应的主要原因,因此及时地从反应体系中去除HCl,对反应的进行非常有利。采取加快搅拌速率,通N2,利用低沸点更多还原

【Abstract】 Over the past decade, there has been a surge of interest in nanomaterials, which include core-shell structures and the self assembly systems. With the progress made on the nanoparticles, the fabrication of uniform hollow capsules with nanometer to micrometer dimensions having tailored structural, optical, and surface properties has become one of the focus points in a wide range of applications. Various procedures have been developed to fabricate these hollow spheres. By far the majority of systems reported are based on micellar or vesicular structures, which principally exhibit a more or less pronounced size and aggregation number fluctuation and which are often subject to shape changes. Form and size invariant polymer hollow spheres were successfully prepared and often exhibit interesting properties, and which may be applicable in broadly ranging technologies. Of particularly these hollow spheres could easily be decorated for the inner or outer surface with different property groups. These hollow spheres are used as confined reaction vessels,drug carriers, dye dispersants, and carrier systems in heterogeneous catalysis et al.. The objective of this work is to develop hollow polysiloxane capsules from emulsion polymerization as well as osmotic swelling approaches for catalytic applications such as heterogeneous catalyst for Heck reaction.This thesis describes the development and optimization of nano capsules using emulsion polymerization-template method、osmotic swelling and stober approaches. The fabrication of Hollow polysiloxane capsule-supported palladium complex has been investigated and their application to the recyclable heterogeneous catalyst for Heck carbonylation of aryl iodides has been reported. Finally, the structure and morphology of hollow polysiloxane capsules have been explored. The thesis presented here involves the following main points:Part one gives an overview of the current state of the art in the field of hollow polymer particles preparation. Both strengths and frailties of the respective preparative methods have been elucidated critically. For clarity the preparative methods is divided into four subsections according to the different approaches that are commonly used to attain the desired particle更多还原